钛氧酞菁的合成工艺研究

以钛酸四丁酯和1,3-二亚氨基异吲哚啉为原料,高收率地合成了钛氧酞菁(TiOPc).分别考察了原料处理方法、反应介质、反应物配比、酞酸四丁酯投料温度及反应时间对产物收率的影响,适宜的合成条件是粗品1,3-二亚氨基异吲哚啉经过w(NaOH)=0.5%的碱性溶液处理,以蒸馏干燥过的邻二氯苯为溶剂,投料比n(1,3-二亚氨基异吲哚啉):n(钛酸四丁酯)=3:1,回流反应3h,收率达到91.26%.     

五氧化二碘辅助亲电碘化1-甲基萘制备高残炭沥青（英文）

以1-甲基萘(1-MNP)为原料,采用碘化/脱碘聚合法成功制备了新型高残炭沥青,研究了溶剂种类、碘化温度和反应物摩尔比对碘化样品的影响。GC-MS结果表明当1-MNP、I_2和I_2O_5以1∶0.75∶0.18的摩尔比在60℃乙酸溶液中反应24 h,碘化产物主要由1-碘-4-甲基萘组成,选择性高达96.4%;碘化样品经130~180℃热处理发生脱碘化氢缩合反应。对所制沥青的甲醇可溶组分分析结果表明,脱碘化氢过程中有芳环加氢产物(四氢萘、5-甲基四氢萘等)和甲基迁移产物(2-甲基萘、二甲基萘、三甲基萘等)生成。通过TG、~1H-NM R和FT-IR等手段对沥青结构进行表征,结果表明该沥青具有较高的聚合度(甲苯可溶组分低于12 wt.%)、较高的残炭率(54~66 wt.%)以及较复杂的甲基萘分子组装方式(包括α-α'、α-β'和β-β')。脱碘聚合显著提高了沥青的聚合度和残炭率,这种沥青可用于高性能炭材料的制备。     

2,6-二乙酰氨基吡嗪-1-氧化物硝化反应研究

研究了2,6-二乙酰氨基吡嗪-1-氧化物在硝硫混酸和发烟硝酸/酸性离子液体中的硝化反应。在混酸硝化体系中,考察了混酸硝化剂类型对产物2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)收率和纯度的影响。在发烟硝酸/N,N,N-三甲基-N-丙磺酸基-硫酸氢铵(TMPSHSO4)硝化体系中,考察了在酸性离子液体催化条件下酸性离子液体使用量、硝解反应温度、酸性离子液体重复使用次数对LLM-105收率和纯度的影响。结果表明:混酸硝化体系中,2,6-二乙酰氨基吡嗪-1-氧化物的最佳硝化剂为KNO3和质量分数20%发烟硫酸,LLM-105的收率为72.5%,质量分数为98.6%。发烟硝酸/酸性离子液体硝化体系中,最佳反应条件为:TMPSHSO4与2,6-二乙酰氨基吡嗪-1-氧化物的物质的量的比为0.051.00,硝解温度为75℃,LLM-105收率为64.8%,质量分数为98.5%,TMPSHSO4经回收可重复使用3次。相对而言,以发烟硝酸/TMPSHSO4为硝化剂合成LLM-105更具优势。用1H NMR、IR和MS对LLM-105的结构进行了表征。     

羧甲基-β-环糊精减水剂的制备与性能

以β-环糊精和氯乙酸为原料,通过亲核取代反应制备了混凝土减水剂羧甲基-β-环糊精(CM-β-CD),讨论了反应物物质的量比、反应温度和反应时间对CM-β-CD的取代度及应用性能的影响。结果表明,当氯乙酸与β-环糊精物质的量比为6∶1、反应温度为60℃、反应时间为5h时,所得CM-β-CD的取代度最大为0.68。水泥净浆实验表明净浆流动度随着取代度的增加而增加,减水剂的最佳掺量为0.8%,减水率为23.5%。红外光谱(FTIR)和核磁共振光谱(NMR)检测结果表明β-环糊精和氯乙酸发生了反应。     

4,4''''-二碘-对-三联苯的合成研究

以对三联苯为原料,经过碘代反应,合成了4,4'-二碘-对-三联苯,经精致提纯,收率为64%;并通过红外光谱验证了产品的结构.     

5-溴-3-叔丁基水杨醛的合成

以2-叔丁基苯酚、镁和多聚甲醛为原料,甲醇为溶剂,经甲酰化反应合成了3-叔丁基水杨醛,再经溴化反应合成了5-溴-3-叔丁基水杨醛.考察了溶剂、反应温度、物料比等对产品收率的影响.5-溴-3-叔丁基水杨醛合成的较优条件为:n(3-叔丁基水杨醛)∶n(液溴)=1∶1.1,反应溶剂为乙醇,反应温度60℃,反应时间8 h,产品经1H-NMR表征确认.     

淀粉与2-氯乙醇醚化反应的研究

对在水溶液中不同反应条件下淀粉与2-氯乙醇醚化的反应进行了研究.考察的因素包括碱处理时间与温度、氢氯化钠及2-氯乙醇的用量以及醚化时间与温度.结果表明,碱处理时间超过40min,摩尔取代度没有明显的变化.摩尔取代度随氢氧化纳用量的增加而提高,但达到最大值后则会降低.随醚化时间的延长,摩尔取代度增大,但10h以后则变化不大.醚化温度在53℃时可以得到较高的摩尔取代度.     

丙烯酸-丁烯醛共聚物的合成

采用水溶液共聚法合成了丙烯酸-丁烯醛共聚物,使用IR、^13C-NMR及DSC表征了共聚物的结构.用称量法测定共聚合反应的转化率和反应速率,乌氏黏度计测定共聚物的特性黏数[η],并用其相对表征共聚物分子量大小.重点研究了共聚合条件对共聚合反应的转化率、反应速率及所得共聚物分子量的影响.实验结果表明,引发剂用量、单体浓度及聚合温度对共聚合反应和共聚物的分子量均有很大影响;丁烯醛对共聚合反应有抑制作用。     

长链纤维素酯在DMAc／LiCl中的均相制备及表征

采用75%乙二胺水溶液对纤维素进行预处理后,以DMAc/LiCl为溶剂,高级脂肪酸为酯化剂,对甲苯磺酰氯为共反应剂在均相状态下合成了纤维素棕榈酸酯和硬脂酸酯。运用红外光谱1、H-NMR、X射线衍射、DSC等手段对产品的结构及性质进行表征,研究了反应时间和反应温度对产物取代度的影响。结果表明,纤维素棕榈酸酯的取代度随反应时间延长和反应温度升高而增大。与纤维素相比,纤维素棕榈酸酯的结晶度下降,而玻璃化转变温度也远低于醋酸纤维素和醋酸丁酸纤维素。纤维素棕榈酸酯和硬脂酸酯分子结构中取代基支链起到了内增塑作用,可改善材料的加工工艺性。     

交联改性苯乙烯-丙烯酸酯树脂纸张表面施胶增强剂的制备及应用

以苯乙烯、丙烯酸丁IR,N-羟甲基丙烯酰胺、丙烯酰胺为原料,用聚乙烯醇(PVA)作为胶体保护剂,采用无皂乳液聚合方式,制备苯乙烯-丙烯酸酯树脂乳液.同时以HDI三聚体与聚乙二醇单甲醚500(MPEG 500)为主要原料制备水分散聚异氛酸酯交联剂.用苯乙烯一丙烯酸酯树脂乳液与亲水改性聚异氛酸酯复合,制备纸张表面施胶增强剂...     

Encapsulation of organic UV ray absorbents into layered double hydroxide for photochemical properties

Organic–inorganic nanohybrids, 3,4-dihydroxycinnamic acid/layered double hydroxide (CA/LDH), 4-hydroxy-3,5-dimethoxycinnamic acid/layered double hydroxide (SA/LDH), and 3-amino-5-triflouromethylbenzoic acid/layered double hydroxide (FBA/LDH) have been synthesized by co-precipitation reaction of organic ultraviolet (UV) ray absorbents such as 3,4-dihydroxycinnamic acid, 4-hydroxy-3,5-dimethoxycinnamic acid, 3-amino-5-triflouromethylbenzoic and Zn₂Al layered double hydroxide (LDH). Detailed structural and absorption properties of the nanohybrids were studied by using X-ray diffraction (XRD), FT-IR and UV-Vis transmittance spectra which revealed that organic UV absorbents have been intercalated into the interlayer spaces of LDH and all nanohybrids showed excellent UV ray absorption. All the nanohybrids showed a lower catalytic activity as compared to the net organic UV ray absorbents by applying air oxidation to castor oil.     

氨基酸酯取代聚膦腈的分子结构和性能关系的研究——(Ⅰ)合成与表征

从分子设计的角度出发,以甘氨酸乙酯、丙氨酸乙酯和苯丙氨酸乙酯为亲核试剂,成功地制备了一系列氨基酸酯单取代和混合取代的聚膦腈。研究了取代反应条件及亲核试剂的添加顺序对聚合物合成及结构的影响,取代反应过程中反应温度、反应时间对氨基酸酯取代度的影响,以及亲核试剂的添加顺序对聚合物合成及结构的影响,其结果为控制合成该类可降解聚合物提供了更多依据。     

Electrochemical destruction of dinitrotoluene isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration process

Mineralization of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by in situ electrogenerated hydrogen peroxide. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including electrode potential, reaction temperature, oxygen dosage and concentration of sulfuric acid. It is worth noting that organic compounds could be completely mineralized by hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of 2,4-DNT and/or 2,6-DNT, 2,4,6-TNT results in o-mononitrotoluene (MNT) and 1,3,5-trinitrobenzene, respectively. Due to the removal of TOC and some amount of water, the electrolytic method established is promising for industrial application to regeneration of spent acid from toluene nitration process.     

Photocatalytic oxidation of 2,4,6-trichlorophenol in water using a cocurrent downflow contactor reactor (CDCR)

The heterogeneous photocatalytic oxidation of aqueous solutions of 2,4,6-trichlorophenol (2,4,6-TCP) as a model pollutant in industrial wastewater has been carried out in a pilot scale cocurrent downflow contactor reactor (CDCR). The reactions were carried out in the presence of Ultra-Violet radiation, O(2) and TiO(2) photocatalyst (VP Aeroperl P25/20). The TiO(2) was characterized by Dynamic Vapour Sorption (DVS) technique giving specific surface area and surface energy of 46.06 m(2)g(-1) and 80.12 mJ m(-2), respectively. The CDC reactor was fitted with an internally and vertically mounted 1.0 kW or 2.0 kW UV lamp. The reactions were carried out at 50 degrees C and 1 bar, with the reactor being operated in closed loop recycle mode and suspended photocatalyst being re-circulated. The CDC reactor, a device of very high mass transfer efficiency giving unusually large gas hold-up of approximately 50%, was operated with oxygen mass transfer and dissolution in the zone above the UV lamp (high mass transfer zone) and along and around the UV lamp housing (reaction zone). Under optimized reaction conditions, 100% conversion of 2,4,6-TCP was achieved in 180 min using 15 dm(3) solutions with initial concentration of 120 mg dm(-3). A combination of TiO(2) photocatalyst, UV irradiation and oxidant was observed to give the most rapid photodegradation and photomineralization of the 2,4,6-TCP in comparison with irradiation only. Using the 1 kW or 2 kW UV lamps, conversion of 100 mg dm(-3) of 2,4,6-TCP after 30 min was 62.51% and 90.71%, respectively, with initial reaction rates of 1.33 x 10(-5) and 4.22 x 10(-5) mol min(-1), respectively, and rate constants 0.0046 and 0.29 min(-1), respectively.     

Quantification of amino acids in fermentation media by isocratic HPLC analysis of their α-hydroxy acid derivatives

In this paper we describe a novel method for quantification of amino acids. First, α-hydroxy acid derivatives of amino acids were formed after reaction with dinitrogen trioxide by the van Slyke reaction. Second, the α-hydroxy acid derivatives were separated on an Aminex HPX-87H column (Bio-Rad) eluted isocratically with 5 mM H(2)SO(4) and quantified by refractive index detection. We were able to measure the reaction products of 13 of the 20 classical amino acids: glycine, l-alanine, l-valine, l-leucine, l-isoleucine, l-methionine, l-serine, l-threonine, l-asparagine, l-glutamine, l-aspartic acid, l-glutamic acid, and l-proline. We obtained linear relationships between the product peak areas and initial amino acid concentration, whereby the concentrations of these amino acids could be quantified on the basis of the quantification of their products. The method can be used to analyze amino acids in parallel with other small molecules, such as sugars or short chain fatty acids, and was used for parallel quantification of glycine, l-alanine, or l-glutamic acid, and glucose uptake in cultures of the heterotrophic dinoflagellate Crypthecodinium cohnii . The method can also be used to quantify other amines, as demonstrated by detection of Tris (2-amino-2-(hydroxymethyl)propane-1,3-diol).     

Direct on-line method to monitor the dynamic structure of noncovalent titanium complexes in solution by using cold-spray ionization time-of-flight mass spectrometry

In this paper, we report the feasibility of using the on-line cold-spray ionization time-of-flight mass spectrometry (CSI-TOFMS) method to monitor directly the labile noncovalent organometallic complexes formed in the substitution reaction between a chiral titanium asymmetric catalyst and organic acid in the toluene solvent. The comparison between the conventional ESI and CSI-TOFMS spectra of [(S)1]2Ti2[(S)2]2 in THF indicated that the CSI-TOFMS is an effective method to characterize the structures of labile organometallic complexes in solution. A new strategy was designed so that [(S)1]2Ti2[(S)2]2 and organic acid solution were delivered independently to the CSI ion source by two infusion syringe pumps, and they mixed at a triple valve, and then the substitution reaction occurred in the sprayer. The mix and reaction time was approximately 5 s and can be adjusted by the length of the PEEK tube and the flow rate. The reaction products were ionized and detected directly by the CSI-TOFMS. Organic acids, such as formic, acetic, phenylpropionic, anisic, and para-methoxylphenylactic acids, were investigated. From the on line CSI-TOFMS spectra, it is observed clearly that one or two (S)2 group(s) can be substituted by the added acid to form new species. The results obtained here demonstrated that the designed strategy with on line CSI-TOFMS is effective and reliable to elucidate the dynamic structure of noncovalent titanium complexes in reaction solution.     

Conformational comparisons between phenoxyacetic acid derivatives in adducts and those in the free form. Part 2

Nine molecular co-crystals containing 2,3-, 2,5-, 2,6- and (3,5-dichlorophenoxy)acetic acid have been prepared and studied using single-crystal X-ray diffraction techniques. The free acid structure of (2,3-dichlorophenoxy)acetic acid is also reported. The bases used to prepare the adducts were 2-aminopyrimidine, 2-amino-2-thiazoline, 2-amino-5-chlorobenzoxazole and 4,4’-dipyridine. The conformations of the phenoxyacetic acid molecules were found in all but one case to be either synclinal (twisted) or antiperiplanar (planar). The one exception was a molecule of (2,6-dichlorophenoxy)acetic acid whose conformation was assigned as anticlinal. General comments are given about the conformational aspects of these and previously reported adducts of phenoxyacetic acid derivatives and how they compare to their free acid structures.     

含苯并噁唑半芳香聚酰胺的合成与表征

为了得到同时具有优良耐热性能和易加工性能的新型半芳香聚酰胺,以5-氨基-2-(对氨基苯)苯并噁唑(ABO)和己二酸基于Yamazaki磷酸化过程合成了聚己二酰对苯撑苯并噁唑二胺(BO6).研究了反应温度对聚合物分子量的影响,并通过FTIR、1H-NMR对其结构进行了表征;利用DSC、TG对其热性能进行了研究.结果表明:反应温度在90℃左右时高聚物获得了最高的粘数.该聚合物的耐热性较脂肪族聚酰胺有较大幅度的提高,同时该聚合物具有较好的耐溶剂性能.     

1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成

以硝基甲烷为原料合成了1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷,总收率为37.8%。采用1HNMR﹑IR和MS对目标产物及中间体的结构进行了表征。在三羟甲基硝基甲烷的合成中,结合反应机理确定了氢氧化钙的用量为:n(CH3NO2)n(Ca(OH)2)=1001;通过对催化剂浓硫酸﹑三氟化硼—乙醚络合物和对甲苯磺酸的比较,得出对甲苯磺酸为中间体2,2-二甲基-5-羟甲基-5-硝基-1,3-二氧杂环己烷合成的较优催化剂;分别采用2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯和2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四对甲苯磺酸酯与NaN3反应,发现磺酸酯基易离去,叠氮化反应更易进行,收率较高;叠氮化反应的较优溶剂为DMSO。DSC分析表明,1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的分解峰温为223.46℃。